JP3247797B2 - Staining agent for yellow coloring - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stain agent for tinting glass, and more particularly to a stain agent for tinting a glass surface to yellow by utilizing ion exchange.

[0002]

2. Description of the Related Art A fog lamp which emits yellow transmitted light is often used as a lamp for running in a fog of an automobile. The yellow coloring of the fog lamp is generally performed by coloring the front glass or the aspherical lens, or covering the light source with a colored cap glass. As a coloring method, a colored glass is processed, a paint mainly composed of solder glass is baked on the surface of a transparent glass, a thin film having a high refractive index / a low refractive index is coated in a multilayer film, or an alkali on the glass surface is coated. There are various methods such as ion exchange of metal ions with ions such as copper and silver, but coloring method by ion exchange, so-called staining method, is considered in consideration of cost, color variation, safety, heat and water resistance, etc. Used.

[0003] Conventionally, as a staining agent for yellow coloring, copper sulfate, sulfates of alkali metals such as sodium sulfate, sulfates of alkaline earth metals such as barium sulfate and zinc sulfate, alumina, zirconate and the like have been used. , Mixed with an inorganic filler powder such as zirconium silicate, and mixed with a mixed oil such as pine oil or terpineol and kneaded into a paste form, which is incorporated into an in-vehicle fog lamp. Alkali metal ions and copper ions in the glass are exchanged by applying and firing on the surface of the aspherical lens or cap glass to be manufactured.

[0004]

However, such a conventional stain agent has a problem that, depending on the composition of the glass, it is difficult to color or the stained surface becomes cloudy and looks whitish when lit. .

The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a stain agent which has a good coloring property on glass and can obtain a clear yellow color without clouding. .

[0006]

Means and Action for Solving the Problems The yellowing stain agent of the present invention comprises 10 to 80% by mass of copper sulfate, 10 to 60% by mass of alkali metal sulfate, and 10 to 60% by mass of alkaline earth metal sulfate. 50 mass% and silicon dioxide 0.1 to 40
% By mass, and 0.05 to 35% by mass of aluminum sulfate
Are respectively blended.

The staining according to the present invention is a method of yellowing transmitted light by the presence of copper ions exchanged with alkali metal ions in the glass, and is easily used as a copper ion supply component at an appropriate firing temperature. Reacting copper sulfate is used. In addition, copper sulfate may be blended in any form, either anhydrous or hydrated.

In the present invention, the compounding ratio of copper sulfate is 10
If the amount is less than mass% t%, ion exchange of copper ions with alkali metal ions is not sufficiently performed and coloring power is poor, so that a desired color tone cannot be obtained. Further, when the mixing ratio is more than 80% by mass, the ratio of other components is relatively small,
It is not preferable because the effects of these components cannot be obtained.

In the present invention, as the sulfate of the alkali metal, sodium sulfate, sodium thiosulfate, potassium sulfate and the like can be used, and sodium sulfate is particularly preferred. These compounds have the function (action) of slightly suppressing the reaction rate during the above-mentioned ion exchange, reducing the roughness of the glass surface, and smoothing the stained surface. Therefore, the mixing ratio of the alkali metal sulfate is 10% by mass.
If the amount is less, the effect of the compounding is almost negligible, and the stained surface becomes rough and rough.
If the amount exceeds 0% by mass, discoloration is hindered and white haze increases, which is not preferable.

As the alkaline earth metal sulfate, barium sulfate, zinc sulfate, calcium sulfate and the like are used. These compounds function to improve the familiarity of the stain agent with the glass surface, enhance the adhesion, and enhance the coloring. The use of zinc sulfate is optimal for obtaining a deep yellow coloration. If the mixing ratio of such an alkaline earth metal sulfate is less than 1% by weight, there is almost no effect, and if it exceeds 50% by mass, cloudiness tends to occur, which is not preferable.

Further, in the present invention, silicon dioxide is used as an inorganic filler. Silicon dioxide not only functions to prevent collapsing when printing and applying a stain agent, prevent shrinkage of the stain agent during firing, and uniform coloration, as well as inorganic fillers such as alumina and zircon. Has the effect of preventing the stained surface from becoming cloudy. And when the compounding ratio of silicon dioxide is less than 0.1% by mass, the effect of addition is almost negligible,
On the other hand, if it exceeds 40% by mass, the glass surface tends to be rough, which is not preferable.

Further, in the present invention, aluminum sulfate is blended in order to enhance coloring and obtain yellow coloring of sufficient density. Aluminum sulfate functions to prevent the glass surface from being roughened. If the blending ratio of aluminum sulfate is less than 0.05% by mass, there is almost no effect. If the blending ratio exceeds 35% by mass, white haze increases and brownish color unevenness occurs, which is not preferable.

In the present invention, the above compounds are each pulverized into a powder and mixed to prepare a stain. In particular, if the powder has a particle size of about 0.05 to 30 μm, it can be uniformly applied without causing clogging at the time of application described later. The pulverization is desirably performed by a wet method using a pot mill or a ball mill and adding an organic solvent such as isopropyl alcohol (IPA) or ethanol.

[0014] The thus prepared stain agent of the present invention is applied to the surface of glass and is heated to an appropriate temperature and fired. The glass used as the base material can be applied to all soft, semi-hard, and hard glasses. In addition, such coating on the glass surface, screen printing,
Spraying, dipping, brush coating, spatula coating, transfer and the like can be used. In order to perform the coating smoothly, it is preferable to knead the material obtained by mixing the powders into a paste using a mixed oil of pine oil, terpineol, cellulose, etc., especially when applying by a method such as spraying or dipping. Preferably, an organic solvent such as IPA is further added to the mixture to reduce the viscosity to an appropriate value.

[0015]

Embodiments of the present invention will be described below.

Example 1 Copper sulfate anhydrous 500 g, sodium sulfate 200 g, barium sulfate 100 g, zinc sulfate 150 g, silicon dioxide 3
0 g, and 20 g of aluminum sulfate,
The resulting powder was put in a pot mill together with 00 cc, pulverized and mixed for 50 hours, dried, sieved with a 100-mesh sieve, and mixed with pine oil 90% by mass, terpineol 5% by mass, and ethyl cellulose 5% by weight mixed oil 500
g was added and kneaded.

Next, the stain agent prepared as described above is printed on a flat portion of the aspherical front glass lens body for fog using a 160-mesh screen.
After drying at 70 ° C. for 10 minutes, the mixture was calcined at 560 ° C. for 60 minutes for ion exchange. After cooling, the residue is washed and removed with JIS.
A front glass lens for fog having an ion exchange layer colored yellow within the D5500 standard was obtained. The chromaticity of the aspherical fog front glass lens thus obtained is shown in FIG.
A-1 in the chromaticity diagram of FIG. Further, the sintering temperature for the ion exchange treatment was set to 570 using the stain agent of the example.
Coating and baking were carried out in the same manner except that the temperature was set at 580 ° C. and 580 ° C. to obtain a yellow colored aspherical front glass lens for fog. The chromaticity of these glass lenses is also shown in FIG.
Are shown together as A-2 and A-3 in the chromaticity diagram. In addition, B-1, B-2, and B-3 in the figure were coated at 560 ° C., 570 ° C., and 580 ° C. after coating in the same manner using a conventional staining agent containing no silicon dioxide and aluminum sulfate. The chromaticity when fired is shown for comparison.

From the chromaticity diagram of FIG. 1, the stained product treated with the stain agent of the embodiment has a darker color under the same baking conditions as compared with the one treated with the conventional stain agent. It can be seen that the degree (yellow) was obtained. In addition, the stained product obtained in the example had clear white clouding when lit, and appeared clear. Further, the stained surface was smooth without roughness.

Examples 2 to 4 The components having the compositions shown in Table 1 were mixed in the same manner as in Example 1 to prepare a stain. Also, for comparison,
A stain was prepared in the same manner as described above, using a composition in which one or both of silicon dioxide and aluminum sulfate were not blended. Next, the stain agent thus obtained was screen-printed on the aspherical front glass lens body for fog in the same manner as in Example 1, heated and fired at 570 ° C. for 60 minutes, and then washed with water to obtain a stained product. Was evaluated by a conventional method for coloring power and white haze. The evaluation results are shown in the lower column of Table 1. In addition, these chromaticities are shown in the chromaticity diagram of FIG.
This is shown as ratio-3 (Comparative Examples 1 to 3).

From the chromaticity diagrams shown in Table 1 and FIG. 2, according to the stain agent of the example, darker chromaticity (colored yellow) was obtained as compared with the case where the stain agent of the comparative example was used, and It turns out that there is little white fogging when it is turned on and it looks clear. The stained surface treated with the stain agent of the example was smooth without glass roughness.

[0021]

[Table 1]

[0022]

As is clear from the above description, according to the yellowing staining agent of the present invention, silicon dioxide is blended as an inorganic filler and aluminum sulfate is blended as an additive. Large yellow tinting strength and deep chromaticity are obtained. In addition, there is little white cloudiness on the stained surface when lit, and it looks clear.

[Brief description of the drawings]

FIG. 1 is a chromaticity diagram of a glass lens treated with the stain agent obtained in Example 1 of the present invention.

FIG. 2 is a chromaticity diagram of a glass lens treated with the stain agent obtained in Examples 2 to 4 of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C03C 1/00-23/00 B60Q 1/20

Claims (2)

(57) [Claims] 1. 10 to 80% by weight of copper sulfate, 10 to 60% by weight of an alkali metal sulfate, 10 to 50% by weight of an alkaline earth metal sulfate, 0.1 to 40% by weight of silicon dioxide, and sulfuric acid 0.05-35% by mass of aluminum,
A yellow coloring stain agent characterized by being blended with each other. 2. The yellow coloring staining agent according to claim 1, wherein each component is mixed in a powder state.